2-Oximino-tetrahydro-1,4-oxazin-3-ones

ABSTRACT

Certain 2-oximino-tetrahydro-1,4-oxazin-3-one and 5-oximino-1,3-oxazolidin-4-one carbamate esters exhibit outstanding miticidal, insecticidal and nematodicial activity; certain 2-oximino-tetrahydro-1,4-oxazin-3-ones and 5-oximino-1,3-oxazolidin-4-ones are useful intermediates in the preparation of pesticidally active carbamate compounds.

This is a division of our prior U.S. application Ser. No. 698,029 filedJune 21, 1976, and now U.S. Pat. No. 4,235,902.

This invention relates to a novel class of compounds and to theirpreparation.

More particularly, this invention relates to a novel class of compoundsof the formula: ##STR1## wherein

Z is hydrogen or ##STR2## wherein:

R₁ and R₁ are:

(a) individually hydrogen, alkyl, alkenyl or alkynyl; or

(b) when R₁ is alkyl, R₂ may also be alkanoyl, trihalomethanesulfenyl,alkylsulfenyl, alkylthiosulfenyl, cycloalkylsulfenyl,cycloalkylthiosulfenyl, or substituted or unsubstituted phenylsulfenylor phenylthiosulfenyl wherein the permissible substituents are one ormore chloro, bromo, fluoro, nitro, cyano, alkoxy or alkyl substituentsin any combination;

R₃ is hydrogen, alkyl, cycloalkyl, alkoxyalkyl or phenyl;

A is methylene or ethylene either unsubstituted or substituted with oneor more alkyl;

Alkyl, alkanoyl, alkynyl, cycloalkyl, alkoxyalkyl and alkenyl moietiesindividually may not include more than 6 carbons.

Preferred because of their higher level of pesticidal activity are thecompounds of this invention wherein:

Z is hydrogen or ##STR3## wherein:

R₁ and R₂ are:

(a) individually hydrogen or alkyl; or

(b) when R₁ is alkyl, R₂ may be alkanoyl or trihalomethanesulfenyl;

R₃ is hydrogen or alkyl;

A is ethylene either unsubstituted or substituted with one or more alkylsubstituents; wherein alkyl or alkanoyl substituents individually mayinclude from 1 to 4 carbons.

The carbamate compounds of this invention are those wherein Z is##STR4## and R₁, R₂, R₃ and A are as described above. These compoundsexhibit outstanding insecticidal activity against such major economicpests as aphid, house fly, Southern armyworm and Mexican Bean Beetle.Certain of these compounds also exhibit excellent nematocidal andmiticidal activity. They are also relatively non-toxic to plants andmammals when used in amounts sufficient to kill insects, nematodes andmites.

This invention also relates to nematocidal, insecticidal and miticidalcompositions comprising an acceptable carrier and a nematocidally,insecticidally or miticidally effective amount of a carbamate compoundof this invention. This invention also includes a method of controllinginsects, nematodes and mites by subjecting them to an insecticidally,nematocidally or miticidally effective amount of a heterocycliccarbamate compound of this invention.

The oxime compounds of this invention are those wherein Z of the aboveformula is hydrogen and R₃ and A are as described above. These compoundsare useful as intermediates in the preparation of insecticidally,nematocidally and miticidally active heterocyclic carbamate compounds.For example, 2-oximino-4-methyltetrahydro-1,4-oxazin-3-one can bereacted with an appropriately substituted carbamoyl halide as forexample, N-methyl-N-trichloromethanesulfenylcarbamoyl fluoride, in thepresence of an acid acceptor such as triethylamine to produce2-[N-trichloromethanesulfenyl-N-methylcarbamoyloximino]-4-methyltetrahydro-1,4-oxazin-3-one,the corresponding pesticidally active heterocyclic carbamate compound.The oxime compounds of this invention can also be reacted with otherchemical species containing electron deficient reaction sites, such asisocyanates or phosgene followed by appropriate amines to preparepesticidally active heterocyclic carbamate compounds. These reactionsare disclosed in more detail below.

The carbamate compounds of this invention can be conveniently preparedemploying a variety of methods which utilize the oxime compounds of thisinvention as precursors. One method for producing the carbamatecompounds of this invention is by reacting the corresponding oxime witha carbonyl halide in the presence of an acid acceptor to form thehaloformate which, is then aminolyzed by reaction with an appropriatelysubstituted amine as illustrated in the following general reactionscheme: ##STR5## In the above reaction scheme R₃ and A are as describedabove. R₁ and R₂ are individually hydrogen, alkyl, alkenyl or alkynyland X is chlorine or fluorine.

Heterocyclic carbamate compounds according to this invention wherein R₂is hydrogen can be prepared by reacting the corresponding oxime with anappropriately substituted isocyanate in the presence of a suitablecatalyst as shown in the following general reaction scheme: ##STR6## Inthe above reaction scheme R₃ and A are as described above and R₁ isalkyl, alkynyl or alkenyl.

The carbamates of this invention can also be prepared by reacting thecorresponding oxime with an appropriately substituted carbamoyl halidein the presence of a acid acceptor as illustrated in the followinggeneral reaction scheme: ##STR7## in which R₁, R₂, R₃ and A are asdefined above and X is chlorine or fluorine.

These reactions are conducted under very similar reaction conditions.Substantially equimolar amounts of the reactants are contacted in aninert solvent. Any inert solvent can be used such as benzene, toluenexylene, dioxane, tetrahydrofuran, ethyl ether, methylene chloride or thelike.

The reactions can be conducted in a heterogeneous phase system or ahomogenous phase system. In the former case, phase transfer agents, suchas crown ethers and quaternary ammonium halides may be used tofacilitate the transfer of reactants across the phase interface.

Reaction temperatures are not critical and may vary widely depending toa large extent on the stability and reactivity of the reagents. Usually,the reaction is conducted at a temperature of from about -10° C. toabout 80° C.

Reaction pressures are not critical. For convenience the reaction isconducted at atmospheric or autogenous pressure.

The reactions illustrated in Methods I and III are conducted in thepresence of an acid acceptor. The acid acceptor employed is a basicmaterial which can be either an organic or an inorganic base. Suitableinorganic bases include alkali metal hydroxides such as sodiumhydroxide, potassium hydroxide or the like. Organic bases which areuseful include organic amines, alkali metal alkoxides or the like.Preferred acid acceptors are tertiary amines, such as pyridine,triethylamine, 1,4-diazabicyclo [2.2.2] octane or the like. In general,the molar ratio of acid acceptor to either reactant is substantiallyequimolar or a slight excess.

The reaction illustrated in Method II is preferably conducted in apresence of a catalyst. Any conventional catalyst of the type commonlyemployed to promote reactions between isocyanate compounds and compoundscontaining an active hydrogen can be used. Preferred catalyst aretertiary amines such as pyridine, triethylamine or the like. Generally,the reaction is conducted in the presence of a quantity of catalystsufficient to provide a suitable and reasonable reaction rate.

Carbamoyl halide precursors can be prepared in accordance with a varietyof conventional methods. N-thiosulfenylated and N-sulfenylated carbamoylfluorides can be prepared by reacting hydrogen fluoride with anappropriately substituted isocyanate to form the mono-substitutedcarbamoyl fluoride which is then reacted with an appropriatelysubstituted thiosulfenyl or sulfenyl N-thiosulfenylated orN-sulfenylated compound respectively. For example, methyl isocyanate canbe reacted with hydrogen fluoride in toluene to form N-methyl carbamoylfluoride which, in turn, can be reacted in situ withp-tert-butylphenylthiosulfenyl chloride in the presence of triethylamineto form N-methyl-N-(p-tert-butylphenylthiosulfenyl) carbamoyl fluoride.

The preparation of N-sulfenylated carbamoyl halides is described in moredetail in U.S. Pat. No. 3,639,471.

The remaining carbamoyl halide percursors, in which R₁ and/or R₂ arebonded to nitrogen through a carbon nitrogen bond can be prepared byreacting an appropriately substituted amine with a carbonyl halide, suchas phosgene.

The heterocyclic oxime precursors, which are novel compounds accordingto this invention are prepared by reacting a corresponding heterocycliclactam with an acid acceptor and a nitrite ester followed byneutralization with acid as illustrated in the following reactionscheme: ##STR8## wherein R₃ and A are as described above.

The reaction is preferably carried out in an inert solvent. Any inertsolvent can be used such as benzene, toluene, xylene, dioxane,tetrahydrofuran, dimethoxyethane, ethyl ether, methylene chloride or thelike.

Illustrative of nitrile esters which are useful are alkyl nitrite esterssuch as ethyl nitrite, isobutyl nitrite or the like.

The acid acceptor employed can be either a strong organic or a stronginorganic base. Suitable organic bases include alkali metal alkoxides,alkylides and the like, and suitable inorganic bases include alkalimetal hydroxides or the like. Alkali metal alkoxides of lownucleophilicity are preferred acid acceptors.

The reaction can be conducted in either a homogenous phase system orheterogeneous phase system. In the latter case phase transfer agents,such as a crown ether or a quaternary ammonium halide, can be used tofacilitate the transfer of reactants across the phase interface.

After the reaction has gone to completion, usually in from about 0.5 hr.to about 20 hours, the oxime salt is neutralized by the addition of anorganic or inorganic acid, such as hydrochloric acid, acetic acid or thelike.

Reaction temperatures are not critical and may be varied widelydepending to a large extent on the stability and reactivity of thereactants. Usually, the reaction is conducted at a temperature of fromabout -70° C. to about 100° C. Reaction pressures are not critical, butusually the reaction is conducted at atmospheric or autogenous pressure.

Heterocyclic lactam precursors used in the preparation of the oximecompounds of this invention can be prepared by reacting an appropriatesubstituted alkanol amine with sodium metal to form the correspondingsodium alkanolate salt which, in turn, is reacted usually in situ withan alkyl alpha-haloalkanoate to achieve cyclization. This procedure isdisclosed in more detail in Example I below. Compounds in which R₃ ishydrogen are readily convertible into the corresponding N-substitutedderivatives via well known conventional methods including but notlimited to; alkylation methods, utilizing reagents such as alkali metalhydroxides and an alkyl halide.

EXAMPLE I Preparation of 4-Ethyltetrahydro-1,4-oxazin-3-one ##STR9##

The Example I compound was prepared according to the followingmodification of the procedure of P. Vieles and J. Sequin (Compt. rend.234, 1980 [1952]). A solution of sodium 2-ethylaminoethylate wasprepared from 178.0 grams of 2-ethylaminoethanol and 46.0 grams ofsodium in 1500 ml of tetrahydrofuran. To this solution was added 246grams of ethyl chloroacetate over approximately 10 minutes whilemaintaining the temperature at -10° to -20° during the addition by meansof external cooling. After one hour at -20°, the reaction mixture wasallowed to warm to ambient temperatures for two hours and then stirredat 70° for 18 hours. The mixture was then cooled to 25° and residualbasicity neutralized by addition of 30 ml of conc. hydrochloric acid.Sodium chloride was then removed by filtration and the filtrate wasvacuum concentrated and distilled to yield 167.3 grams of the product,bp. 75°-78°/0.01 mm. Carbonyl infrared absorption at 6.05μ and theabsence of bands in the carbonyl region at wavelengths below 6.0μconfirmed lactam rather than lactone ring formation. NMR (Acetone, δ):1.08, triplet, CH₃ ; 3.88, Quartet, CH₂ (CH₃); 3.98, singlet, CH₂ (CO);3.33, triplet, NCH₂ (CH₂ O), 3.84, triplet, OCH₂ (CH₂ N).

Anal. Calc'd for C₆ H₁₁ NO₂ : C, 55.80; H, 8.58; N, 10.84; Found: C,54.84; H, 8.18; N, 10.57.

EXAMPLE II Preparation of 4-Methyl-5-ethyltetrahydro-1,4-oxazine-3-one##STR10##

A solution of the crude intermediate4-methyl-5-ethyl-tetrahydro-1,4-oxazine-3-one was prepared in a mannersimilar to that described in Example I by reacting the sodium salt of2-amino-butan-1-ol (from 240 g of the amino alcohol and 62 grams ofsodium) in 2500 ml of tetrahydrofuran with 338 g of ethyl chloroacetatefollowing alcohol and 62 grams of sodium) in 2500 ml evaporation of thereaction solvent, the crude product was taken up in chloroform andwashed with water. After drying the organic solution and removal of thesolvent, recrystallization of the crude product from isopropylether/ethyl acetate yielded 151 grams of5-ethyl-tetrahydro-1,4-oxazin-3-one, m.p. 70°-73°. Absence of carbonylabsorption bands in the infrared in the lactone region and the presenceof a strong band at 6.10μ confirmed lactam rather than lactonecyclisation. Other major IR bands: 3.42, 3.52, 6.7, 6.8, 7.0, 7.2, 7.5,7.8, 8.0, 8.7, 8.9, 8.98, 9.2, 9.5, 10.1, 10.5, 10.9, 11.8, 12.4 and13.8μ NMR(CDCl₃, δ): 2.95, singlet, NCH₃ ; 3.2, multiplet, N-CH(CH₂CH₃); 1.75, quintet, CH₂ (CH₃); 0.93 triplet, CH₃ (CH₂); 3.78 and 3.84,AB pair, CH₂ O; 4.07 singlet, CH₂ CO.

Methylation of the secondary lactone by reaction with one equivalent ofsodium hydroxide and excess methyl iodide in dimethoxyethane afforded,after conventional workup and vacuum distillation, 55 grams of4-methyl-5-ethyltetrahydro-1,4-oxazin-3-one, by 68°-72°/0.10 mm.

Anal: Calc'd for C₇ H₁₃ NO₂ : C, 55.79; H, 8.58; N, 10.84; Found: C,54.43; H, 8.05; N, 10.53.

EXAMPLE III Preparation of 2-Oximino-4-methyltetrahydro-1,4-oxazin-3-one##STR11##

While maintaining the temperature near -55°, a solution of 11.5 grams of4-methyltetrahydro-1,4-oxazin-3-one dissolved in 100 ml of anhydroustetrahydrofuran was added over a period of twenty minutes to a slurry of14.6 grams of potassium t-butoxide in 100 ml of tetrahydrofuranvigorously stirring under a nitrogen atmosphere. After equilibrating theresultant mixture for 30 minutes at -60°, a solution of 11.4 grams ofisobutyl nitrite in 50 ml of tetrahydrofuran was added over 15 minuteswhile maintaining the temperature at -60° with external cooling. After a15-minute equilibration at -60°, the reaction mixture was brought to 25°and stirred for 3 hours. The solution was then cooled to 0° andneutralized to pH 5 with 65 ml of a solution of 18 ml of conc.hydrochloric acid diluted to 100 mls. with absolute ethanol. After a15-minute equilibration, potassium chloride was filtered off and thesolvent removed in vacuuo. The resulting oil was triturated with 50 mlof ethyl acetate and the resulting solid was collected and thenrecrystallized from 150 ml. of acetonitrile yielding 5.07 g of the oximeproduct, mp. 199°-201°.

Anal: Calc'd for C₅ H₈ N₂ O₃ : C, 41.67; H,5.59; N, 19.43; Found: C,41.17; H, 5.49; N, 1920.

EXAMPLE IV Preparation of2-Oximino-4-methyl-5-ethyltetrahydro-1,4-oxazin-3-one ##STR12##

A quantity of 33.7 g of potassium t-butoxide, 40.0 g of4-methyl-5-ethyl-tetrahydro-1,4-oxazin-3-one, and 29.3 g of isobutylnitrite were caused to react sequentially in 800 ml of anhydroustetrahydrofuran in a manner similar to that described in Example III.Following a similar workup, 44.7 g of a thick oil were obtained whichcould not be induced to crystallize. Part (10 grams) was chromatographedon silica gel eluting the product band (3.0 grams) with acetone afterunchanged starting material (5.4 grams) had been eluted with isopropylether/acetone mixtures. Trituration of the product fraction with ethylacetate afforded pure oxime product, 2.9 g, mp. 168.5°-170.0°,equivalent to a total yield (in 44.7 g of crude product) of 13.0 grams.

Anal: Calc'd for C₇ H₁₂ N₂ O₃ : C, 48.83; H, 7.02; N, 16.27; Found: C,47.11; H, 7.01; N, 15.76. EXAMPLE V

Preparation of 2-Methylcarbamoyloximino-4-methyltetrahydro1,4-oxazin-3-one ##STR13##

To a slurry of 2.9 grams of2-oximino-4-methyltetrahydro-1,4-oxazin-3-one and 25 microliters oftriethylamine in 150 ml of acetonitrile magnetically stirred in a 300 mlpressure bottle was added, in portions at the rate 0.5 ml/15 mins., 10ml of a solution of 3.2 ml of methylisocyanate in 16.8 ml ofacetonitrile. After stirring the resultant solution for 72 hours, thesolution was treated with carbon black, filtered, and the solventevaporated. Trituration with a mixture of ethyl acetate and isopropylether afforded 3.9 grams of the product, mp 177°-9°.

Anal: Calc'd for C₇ H₁₁ N₃ O₄ ; 1/2H₂ O: C, 40.00; H, 5.75; N, 19.99;Found: C, 39.99; H, 5.61; N, 19.77.

EXAMPLE VI Preparation of2-[N-Trichloromethanesulfenyl-N-methylcarbamoyloximino]-4-methyltetrahydro-1,4-oxazin-3-one##STR14##

A quantity of 2.53 g. of 2-oximino-4-methyltetrahydro-1,4-thiazin-3-oneand 4.9 g of N-methyl-N-trichloromethansulfenylcarbamoyl fluoride (WestGerman Pat. No. 1,297,095; Farbenfabriken Bayer, A. G., June 12, 1969)and 1.5 ml of triethylamine in 175 ml of tetrahydrofuran were caused toreact in a manner similar to that described forN-trichloromethanesulfenyl-N-methylcarbamates in Netherlands Pat. No.7,404,474, Union Carbide Corporation, July 10, 1974. Conventional workupand recrystallization from acetone/isopropyl ether afforded 4.0 g of theproduct, mp 166°-168°.

Anal: Calc'd for C₈ H₁₀ Cl₃ N₃ O₄ S: C, 27.41; H, 2.87; N, 11.98; Found:C, 27.41; H, 2.75; N, 11.92.

EXAMPLE VII Preparation of2-[N-Trichloromethanesulfenyl-N-methyl/carbamoyloximino]-4,5,5-trimethyltetrahydro-1,4-oxazin-3-one##STR15##

In a manner similar to that described in Example VI, 1.5 g of2-oximino-4,5,5-trimethyltetrahydro-1,4-oxazin-3-one, 2.2 g ofN-methyl-N-trichloromethanesulfenylcarbamoyl fluoride and 1.40 ml oftriethylene were caused to react in 350 ml of tetrahydrofuran.Conventional workup and recrystallization from acetone/isopropyl etherafforded 1.46 g of product, mp 165°-166°.

Anal: Calc'd for C₁₀ H₁₄ Cl₃ N₃ O₄ S: C, 31.72; H, 3.73; N, 11.09;Found: C, 31.47; H, 3.55; N, 11.12.

EXAMPLE VIII Preparation of2-Methylcarbamoyloximino-4,-6-dimethyltetrahydro-1,4-oxazin-3-one##STR16##

In a manner similar to that described in Example V, 0.5 grams of2-oximino-4,6-dimethyltetrahydro-1,4-oxazin-3-one, 10 ml oftriethylamine and 0.25 ml of methyl isocyanate were caused to react inacetonitrile. Conventional workup and trituration with isopropylether/ethyl acetate afforded 0.650 grams of2-methylcarbamoyloximino-4,6-dimethyltetrahydro-1,4-oxazin-3-one, mp.170°-173°.

Anal: Calc'd for C₈ H₁₃ N₃ O₄ : C, 44.65; H, 6.09; N, 19.53; Found: C,43.73; H, 5.64; N, 19.07.

The following compounds are representative of other compounds that arewithin the scope of this invention which can be prepared according tothis invention by selecting appropriate starting materials for use inthe procedures described above:

4,5-Dimethyl-2-(N,N-dimethylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Propyl-2-butylcarbamoyloximino-tetrahydro-1,4-oxazin-3-one

4,6-Dimethyl-2-(n-butylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Methyl-2-[N-(t-butylthiosulfenyl)-N-methylcarbamoyloximino]tetrahydro-1,4-oxazin-3-one.

4-Methyl-2-[N-(4-t-butylphenylthiosulfenyl)-N-methylcarbamoyloximino]tetrahydro-1,4-oxazin-3-one

4-Methyl-2-(N-allylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Methyl-2-propargylcarbamoyloximino-tetrahydro-1,4-oxazin-3-one

4,5,6-Trimethyl-2-[N-(4-cyanophenylthiosulfenyl)-N-methylcarbamoyloximino]tetrahydro-1,4-oxazin-3-one

4-Cyclohexyl-2-[N-(4-methoxyphenylsulfenyl)-N-methylcarbamoyloximino]tetrahydro-1,4-oxazin-3-one

4-Allyl-2-[N-(4-tert-butylphenylsulfenyl)-N-methylcarbamoyloximino]tetrahydro-1,4-oxazin-3-one

4-Cyclopentanyl-2-(N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-(2-Methoxyethyl)-2-(N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Methyl-2-(N-trifluoromethanesulfenyl-N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Methyl-2-[N-(2,4-dichlorophenylsulfenyl)-N-methylcarbamoyloximino]tetrahydro-1,4-oxazin-3-one

4-Methyl-2-(N-phenylthiosulfenyl-N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

2,3-Dimethyl-5-(N-methylcarbamoyloximino)-1,3-oxazolidin-4-one

2-(N-Propylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Propenyl-2-(N-methylcarbamoyloximino)-tetrahydro-1,4-oxazin-3-one

4-Hexyl-2-(N-methylcarbamoyloximino)-tetrahydro-1,4-oxazin-3-one

4-Isopropyl-2-(N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Cyclopropyl-2-(N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4,5,5,6,6-Pentamethyl-2-(N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-(2-Hexenyl)-2-[N-hexylthio-N-ethylcarbamoyloximino]-1,4-oxazin-3-one

4-Methyl-2-[N-hexylthiosulfenyl-N-methylcarbamoyloximino]-1,4-oxazin-3-one

4-Phenyl-2-[N-hexanoyl-N-methylcarbamoyloximino]-1,4-oxazin-3-one.

4-Methyl-2-(N-acetyl-N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Ethyl-2-(carbamoyloximino)tetrahydro-1,4-oxazin-3-one

4-Methyl-2-(N-hexyl-N-methylcarbamoyloximino)tetrahydro-1,4-oxazin-3-one

Suspensions of the test compounds were prepared by dissolving one gramof compound in 50 milliliters of acetone in which had been dissolved 0.1gram (10 percent of the weight of compound) of an alkylphenoxypolyethoxyethanol surfactant, as an emulsifying or dispersing agent. Theresulting solution was mixed into 150 milliliters of water to giveroughly 200 milliliters of a suspension containing the compound infinely divided form. The thus-prepared stock suspension contained 0.5percent by weight of compound. The test concentrations in parts permillion by weight employed in the tests described hereinbelow wereobtained by appropriate dilutions of the stock suspension with water.The test procedures were as follows:

Bean Aphid Foliage Spray Test

Adults and nymphal stages of the bean aphid (Aphis fabae Scop.) rearedon potted dwarf nasturtium plants at 65°-70° F. and 50-70 percentrelative humidity, constituted the test insects. For testing purposes,the number of aphids per pot was standardized to 100-150 by trimmingplants containing excess aphids.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation.

The potted plants (one pot per compound tested) infested with 100-150aphids, were placed on a revolving turntable and sprayed with 100-110milliliters of test compound formulation by use of a DeVilbiss spray gunset at 40 psig. air pressure. This application, which lasted 25 seconds,was sufficient to wet the plants to run-off. As a control, 100-110milliliters of a water-acetone-emulsifier solution containing no testcompound were also sprayed on infested plants. After spraying, the potswere placed on their sides on a sheet of white standard mimeograph paperwhich had been previously ruled to facilitate counting. Temperature andhumidity in the test room during the 24 hour holding period were 65°-70°F. and 50-70 percent, respectively. Aphids which fell onto the paper andwere unable to remain standing after being uprighted were considereddead. Aphids remaining on the plants were observed closely for movementand those which were unable to move the length of the body uponstimulation by prodding were considered dead. Percent mortality wasrecorded for various concentration levels.

Southern Armyworm Leaf Spray Test

Larvae of the southern armyworm (Prodenia eridania, (Cram.)), reared onTendergreen bean plants at a temperature of 80°±5° F. and a relativehumidity of 50±5 percent, constituted the test insects.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation. Potted Tendergreen bean plants ofstandard height and age were placed on a revolving turntable and sprayedwith 100-110 milliliters of test compound formulation by use of aDeVilbiss spray gun set at 10 psig air pressure. This application, whichlasted 25 seconds, was sufficient to wet plants to run-off. As acontrol, 100-110 milliliters of a water-acetone-emulsifier solutioncontaining no test compound were also sprayed on infested plants. Whendry, the paired leaves were separated and each one was placed in a 9centimeter Petri dish lined with moistened filter paper. Five randomlyselected larvae were introduced into each dish and the dishes wereclosed. The closed dishes were labeled and held at 80°-85° F. for threedays. Although the larvae could easily consume the whole leaf withintwenty-four hours, no more food was added. Larvae which were unable tomove the length of the body, even upon stimulation by prodding, wereconsidered dead. Percent mortality was recorded for variousconcentration levels.

Mexican Bean Beetle Leaf Spray Test

Fourth instar larvae of the Mexican bean beetle (Epilachna varivestis,Muls.), reared on Tendergreen bean plants at a temperature of 80°±5° F.and 50±5 percent relative humidity, were the test insects.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation. Potted Tendergreen bean plants ofstandard height and age were placed on a revolving turntable and sprayedwith 100-110 milliliters of test compound formulation by use of aDeVilbiss spray gun set at 10 psig air pressure. This application, whichlasted 25 seconds, was sufficient to wet plants to run-off. As acontrol, 100-110 milliliters of a water-acetone-emulsifier solutioncontaining no test compound were also sprayed on infested plants. Whendry, the paired leaves were separated and each was placed in a 9centimeter Petri dish lined with moistened filter paper. Five randomlyselected larvae were introduced into each dish, and the dishes wereclosed. The closed dishes were labeled and held at a temperature of80°±5° F. for three days. Although the larvae could easily consume theleaf within 24 to 48 hours, no more food was added. Larvae which wereunable to move the length of the body, even upon stimulation, wereconsidered dead.

Fly Bait Test

Four to six day old adult house flies (Musca domestica, L.), rearedaccording to the specifications of the Chemical SpecialitiesManufacturing Association (Blue Book, McNair-Dorland Co., N.Y. 1954;pages 243-244, 261) under controlled conditions of 80°±5° F. and 50±5percent relative humidity, were the test insects. The flies wereimmobilized by anesthetizing with carbon dioxide and twenty fiveimmobilized individuals, males and females, were transferred to a cageconsisting of a standard food strainer above five inches in diameterwhich was inverted over a wrapping-paper-covered surface. The testcompounds were formulated by diluting the stock suspension with a 10percent (by weight) sugar solution to give a suspension containing 500parts of test compound per million parts of final formulation, byweight. Ten milliliters of the test formulation were added to a soufflecup containing a one-inch square of an absorbent cotton pad. This baitcup was introduced and centered on the blotting paper under the foodstrainer prior to admitting the anesthetized flies. The caged flies wereallowed to feed on the bait for twenty four hours, at a temperature of80°±5° F. and the relative humidity of 50±5 percent. Flies which showedno sign of movement on prodding were considered dead.

Mite Foliage Spray Test

Adults and nymphal stages of the two-spotted mite (Tetranychus urticaeKoch), reared on Tendergreen bean plants at 80±5 percent relativehumidity, were the test organisms. Infested leaves from a stock culturewere placed on the primary leaves of two bean plants six to eight inchesin height, growing in a two-and-a-half inch clay pot. 150-200 Mites, asufficient number for testing, transferred from the excised leaves tothe fresh plants in a period of twenty four hours. Following the twentyfour hour transfer period, the excised leaves were removed from theinfested plants. The test compounds were formulated by diluting thestock suspension with water to give a suspension containing 500 parts oftest compound per million parts of final formulation. The potted plants(one pot per compound) were placed on a revolving turntable and sprayedwith 100-110 milliliters of test compound formulation by use of aDeVilbiss spray gun set at 40 psig. air pressure. This application,which lasted 25 seconds, was sufficient to wet the plants to run-off. Asa control, 100-110 milliliters of a water solution containing acetoneand emulsifier in the same concentrations as the test compoundformulation, but containing no test compound, were also sprayed oninfested plants. The sprayed plants were held at 80±5 percent relativehumidity for six days, after which a mortality count of motile forms wasmade. Microscopic examination for motile forms was made on the leaves ofthe test plants. Any individual which was capable of locomotion uponprodding was considered living.

Nematocide Test

The test organism used was the infective migratory larvae of theroot-knot nematode, Meloidogyne incognita var. acrita, reared in thegreenhouse on roots of cucumber plants. Infected plants were removedfrom the culture, and the roots are chopped very finely. A small amountof this inoculum was added to a pint jar containing approximately 180cc. of soil. The jars were capped and incubated for one week at roomtemperature. During this period eggs of the nematode were hatched, andthe larval forms migrated into the soil.

Ten ml. of the test formulation were added to each of the two jars foreach dosage tested. Following the addition of chemical, the jars werecapped, and the contents thoroughly mixed on a ball mill for 5 minutes.

The test compounds were formulated by a standard procedure of solutionin acetone addition of an emulsifier, and dilution with water. Primaryscreening tests were conducted at 3.33 m.g. of the test compound perjar.

The jars were left capped at room temperature for a period of 48 hours,and the contents then transferred to 3 inch pots. Subsequently, the potswere seeded to cucumber as an indicator crop and placed in thegreenhouse where they were cared for in the normal fashion forapproximately 3 weeks.

The cucumber plants were then taken from the pots, the soil removed fromthe roots, and the amount of galling visually rated.

The results of these tests are set forth in Table I below. In thesetests the pesticidal activity of the compounds against aphid, mite,Southern Armyworm, Mexican Bean Beetle, nematodes and house fly wasrated as follows:

A=excellent control

B=partial control

C=no control

Dashes indicate no test conducted.

Certain of these compositions were also evaluated to determine theirperoral toxicity to mammals. The animal selected for this experiment wasthe art. The test results obtained are expressed in terms of the numberof milligrams of compositions per kilogram of weight of the animalrequired to achieve a mortality rate of 50 percent (LD₅₀).

The results of all of these tests are set forth in Table I below:

                                      TABLE I                                     __________________________________________________________________________                                Biological Activity                                                                  Southern                                                                             Bean           Acute oral           Structure           m.p.°C.                                                                        Aphid                                                                             Mite                                                                             Army Worm                                                                            Beetle                                                                            Housefly                                                                           Nematode                                                                            Rat                  __________________________________________________________________________                                                             mg/kg                 ##STR17##          177-179°                                                                       A   A  A      A     A  A     343.0                 ##STR18##          166-168°                                                                       A   B  C      A     A  A     --                    ##STR19##          124-125°                                                                       A   A  C      A     A  A     126.0                 ##STR20##            165-166.5°                                                                   A   A  C      B     A  --    794.0                 ##STR21##          123.5-124.5°                                                                   A   A  A      C     A  C      23.8                 ##STR22##          144-146°                                                                       A   A  C      A     A  A     --                    ##STR23##          88-89°                                                                         A   A  C      C     A  C     --                    ##STR24##          --      A   C  C      C     A  --    --                    ##STR25##          170-173°                                                                       A   A  A      A     A  A     --                    ##STR26##          70-79°                                                                         A   A  A      B     A  C                          __________________________________________________________________________

The compounds contemplated in this invention may be applied asinsecticides, miticides and nematocides according to methods known tothose skilled in the art. Pesticidal compositions containing thecompounds as the active toxicant will usually comprise a carrier and/ordiluent, either liquid or solid.

Suitable liquid diluents or carriers include water, petroleumdistillates, or other liquid carriers with or without surface activeagents. Liquid concentrates may be prepared by dissolving one of thesecompounds with a nonphytotoxic solvent such as acetone, xylene, ornitrobenzene and dispersing the toxicants in water with the acid ofsuitable surface active emulsifying and dispersing agents.

The choice of dispersing and emulsifying agents and the amount employedis dictated by the nature of the composition and the ability of theagent to facilitate the dispersion of the toxicant. Generally, it isdesirable to use as little of the agent as is possible, consistant withthe desired dispersion of the toxicant in the spray so that rain doesnot re-emulsify the toxicant after it is applied to the plant and washit off the plant. Nonionic, anionic, amphoteric or cationic dispersingand emulsifying agents may be employed, for example, the condensationproducts of alkylene oxides with phenol and organic acids, alkyl arylsulfonates, complex ether alcohols, quaternary ammonium compounds, andthe like.

In the preparation of wettable powder or dust or granulatedcompositions, the active ingredient is dispersed in and on anappropriately divided solid carrier such as clay, talc, bentonite,diatomaceous earth, fullers earth, and the like. In the formulation ofthe wettable powders the aforementioned dispersing agents as well aslignosulfonates can be included.

The required amount of the toxicants contemplated herein may be appliedper acre treated in from 1 to 200 gallons or more of liquid carrierand/or diluent or in from about 5 to 500 pounds of inert solid carrierand/or diluent. The concentration in the liquid concentrate will usuallyvary from about 10 to 95 percent by weight and in the solid formulationsfrom about 0.5 to about 90 percent by weight. Satisfactory sprays,dusts, or granules for general use contain from about 1/4 to 15 poundsof active toxicant per acre.

The pesticides contemplated herein prevent attack by insects, nematodesand mites upon plants or other material to which the pesticides areapplied, and they have relatively high residual toxicity. With respectto plants, they have a high margin of safety in that when used insufficient amount to kill or repel the insects, they do not burn orinjure the plant, and they resist weathering which includes wash-offcaused by rain, decomposition by ultra-violet light, oxidation, orhydrolysis in the presence of moisture or, at least such decomposition,oxidation, and hydrolysis as would materially decrease the desirablepesticidal characteristic of the toxicants or impart undesirablecharacteristics, for instance, phytotoxicity, to the toxicants. Thetoxicants are so chemically inert that they are now compatible withsubstantially any other constituents of the spray schedule, and they maybe used in the soil, upon the seeds, or the roots of plants withoutinjuring either the seeds or roots of plants. They may also be used incombination with other pesticidally active compositions.

What is claimed is:
 1. A compound of the formula: ##STR27## wherein: Zis hydrogen;R₃ is hydrogen, alkyl, cycloalkyl, alkoxyalkyl or phenyl; Ais ethylene either unsubstituted or substituted with one or more alkyl;wherein the alkoxyalkyl, alkyl or cycloalkyl moieties individually maynot contain more than 6 carbons.
 2. A compound according to claim 1wherein R₃ is hydrogen or alkyl.
 3. A compound according to claim 1wherein A is unsubstituted ethylene.
 4. A compound according to claim 1wherein A is ethylene substituted with one or more methyl or ethylsubstituents in any combination. 5.2-Oximino-4,6-dimethyl-tetrahydro-1,4-oxazin-3-one. 6.2-Oximino-4,5,5-trimethyltetrahydro-1,4-oxazin-3-one.